Classifications

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  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
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  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
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  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/443—Particulate material
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  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0082—Organic polymers
• • H—ELECTRICITY
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  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties

Definitions

• the invention generally concerns electrodes, ion conductive assemblies, and energy storage units comprising same.
• the cathode active material can vary between various lithium salts and oxides such as LiFePQt (Lithium ferro phosphate), NMC (Lithium Nickel Manganese Cobalt oxide), NCA (Lithium Nickel cobalt aluminum oxide) and others.
• Each of the electrodes may also contain conductive additives such as carbon black, graphite, carbon nanotubes, reduced graphene oxide and others, and a binder which connects the particles to each other (cohesion), and to the current collectors (adhesion).
• each of these electrodes and separator comprises, in most cases, two continues phases:
• solid phase comprising the active material, conductive additives, and a binder
• voids exhibit a porosity of between 30%-43% for the electrodes, and 20-80% for the separation area.
• This structure ensures full connectivity within the solid phase and between the solid phase and the current collector.
• a full connectivity of the electrolyte solution with the active material ensures full exploitation of the surface area of the active material, i.e. effective surface area for ion transport between the electrolyte solution and the active material and between the entire network of voids.
• silicon has been found to offer up to 10 times more energy density as compared to a carbon anode.
• silicon suffers from three major drawbacks: (1) low electronic conductivity with a high electric conductivity variation between different state of charges (SOC), especially above 70% and below 5% SOC. This necessitates a considerable amount of conductive additives, which results in a massive solid electrolyte interface (SEI) built on their surface.
• SEI solid electrolyte interface
• the main initial loss of lithium in the system is due to its consumption as a building blocks (lithium oxide, lithium carbide and more) during SEI generation. This leads to increased resistivity during cycle life, and hence capacity drop.
• a different approach is to use lithium ion conductive binders which coat the active material and change its form along with the active material expansion/retraction mechanism during charge and discharge operation. This is typically done alongside limiting the access of the electrolyte solution from a direct contact with the active material.
• Low first cycle efficiency and low total efficiency are typically due to factors such as contact between the electrolyte solution and the active material and a large surface area of the ion conductive polymer. Both are highly reactive towards the electrolyte solution, resulting in SE1 formation.
• the initial capacity is a sum of the metalloid internal capacity with lithium, together with the pseudo capacity measured due to the energy transfer during the SEI formation. Where the fraction of the energy loss due to the SEI formation in the sum above reduces from cycle to cycle, and where until this side reaction stops (or more likely becomes negligible), lithium in the system is transferred into a non-returnable lithium.
• US Patent No. 6,027,836 [4J discloses a non-aqueous polymer cell that contains a lithium ion conductive polymer having a porosity in the range of 10 % to 80 %. In the cell the electrolyte is held not only in the pores of the microporous polymer but also within the polymer itself.
• the inventors of the technology disclosed herein have developed a methodology that cures the deficiencies of the art and provides a novel energy storage system that makes use of a novel ion conductive assembly and electrodes.
• ICA ion conductive assembly
• the invention provides an ion conductive assembly (ICA) comprising a plurality (two or more) of material regions, said plurality of material regions being linked by a polymeric amorphous network of at least one ion conductive material, wherein
• the ion conductive material in a first region (of the two or more or plurality of regions) defining an electrode (which may be an anode or a cathode), is of a porosity up to 20% and comprises a plurality of active materials fully embedded within the ion conductive material, and wherein
• the ion conductive material in a second region defining a separator, is of a porosity of between 0 and 80%, and free of active materials and electron conductive additives.
• the number of material regions in an ICA according to the invention may vary based on the structure of the device. Typically, the number of material regions is at least two, or the number of material regions is two or three or four, etc. In some embodiments, the number of material regions is two or three. Where the number of regions is two, one of the two regions is an electrode (anode or cathode) and the second of the two regions is a separator region, as defined. Where the number of regions is three or three or more, one of the three (or three or more) regions is an electrode and a second of the three (or three or more) regions is a separator region, as defined. The nature of the third (or further) region may vary.
• one region is an anode
• a second region is a cathode
• a third region is a separator that is interposed (positioned) between the anode and the cathode.
• the first region being the electrode region
• the second region namely the separator region
• a degree or level of porosity that is up to 20% (the porosity being different from zero) for the electrode region and is between 0 and 80% for the separator region.
• The“ degree or level of porosity” refers to the fractional area of the region that is composed of pores, e.g., material-free areas, from the total area of the region, as a percentage between 0 and 20% or between 0 and 80%, as defined.
• the porosity of a region may be determined by any conventional means available in the art or may be calculated based on measurements as below. The porosity may be calculated by:
• the porosity In cases when the observed density of the material equals the bulk density of the material, the porosity is regarded at zero percent (0%). Similarly, when the observed density is 80% of the bulk density, the porosity is 20%, when the observed density is 50% of the bulk density, the porosity is 50%, and when the observed density is 20% of the bulk density, the porosity is 80%.
• the expression“up to 20%” refers to a degree or level of porosity that is lower than 20%, but may also be 20%.
• the porosity of the two regions may be same or different. Wherein the degree or level of porosity is of each of the regions is the same or of a similar value, the regions are distinguishable from one another by the presence or absence of active materials and electron conductive additives.
• the first region, being the electrode region, and the second region, being the separator region may be each characterized by a similar or identical porosity level (i.e., wherein the porosity of one is between 0% and 20% and of the other is between 0% and 80%), and differentiated one from another by one or more active materials or electron conductive additives that are present in one and absent in the other (or present in different amounts in both regions).
• a similar or identical porosity level i.e., wherein the porosity of one is between 0% and 20% and of the other is between 0% and 80%
• the level of porosity of the electrode region is between 0 and 20%, 0 and 19%, 0 and 18%, 0 and 17%, 0 and 16%, 0 and 15%, 0 and 14%, 0 and 13%, 0 and 12%, 0 and 11%, 0 and 10%, 0 and 9%, 0 and 8%, 0 and 7%, 0 and 6%, 0 and 5%, 0 and 4%, 0 and 3%, 1 and 20%, 1 and 19%, 1 and 18%, 1 and 17%, 1 and 16%, 1 and 15%, 1 and 14%, 1 and 13%, 1 and 12%, 1 and 11%, 1 and 10%, 1 and 9%, 1 and 8%, 1 and 7%, 1 and 6%, 1 and 5%, 1 and 4%, 1 and 3%, 1 and 2%, 5 and 20%, 5 and 15%, 5 and 10%, 10 and 20%, or 10 and 15%.
• the degree of porosity of the electrode region is below and different from
• the separator has a porosity of 0 and 80%. In some embodiments, the porosity is greater than 0 % but is different from 20%. In some embodiments, the separator porosity is between 0 and 80%, 0 and 75%, 0 and 70%, 0 and 65%, 0 and 60%, 0 and 55%, 0 and 50%, 0 and 45%, 0 and 40%, 0 and 35%, 0 and 30%, 30 and 80%, 40 and 80%, 50 and 80%, 60 and 80%, 70 and 80%, 30 and 70%, 30 and 60%, 30 and 50%, 30 and 40%, 40 and 80%, 40 and 70%, 40 and 60%, 50 and 80%, or 50 and 70%. In some embodiments, the level of porosity is between 40 and 60%.
• the innovative ICA of the invention can be used with any kind of electrode (anode and/or cathode) material composition and/or separator material composition where it offers the following advantages over known technologies:
• the ICA can be expended to all-solid-state or semi-solid-state full cells.
• the ICA can be further used as energy storage binders for electrodes and/or separators.
• the electrode and the separator are linked by a polymeric amorphous network of an ion conductive material (hereinafter “ion conductive continuous phase” or“ continuous phase”), which, at a region defining the electrode, is of low porosity (below or up to 20%) and comprises a plurality of active materials, e.g., in particulate form(s), that are fully embedded within the continuous phase.
• the continuous phase comprises high porosity (being as high as 80% in certain embodiments) and is free of active materials and electron conductive additives.
• This region characterized by high porosity and absence of active materials is hereinafter referred to as the“ porous phase”.
• Both the continuous phase and the porous phase exhibit material continuity. Independent of whether or not both phases (the region defining the electrode and the region defining the separator) are formed of the same or different material(s), a clear boarder defining the limits of both phases cannot be established. Both phases are adhesively associated such that mechanical separation is not possible.
• the ion conductive material of the first region is the same as the ion conductive material of the second region (the separator). In some other embodiments, the ion conductive material of the first region is different from the ion conductive material of the second region.
• the electrode of the invention is constructed of a low porosity continuous ion conductive polymeric material, which defines an ion mobility path, and one or mere active materials, e.g., in the form of particles, that are embedded, encapsulated, coated or surrounded by the polymeric material.
• the electrode is configured to allow ion mobility through the low porosity continuous phase towards the active material.
• the active material is protected from direct contact with any fluid contained in the porous phase, e.g., an electrolyte solution.
• This protective feature increases or greatiy improves the efficiency of the ICA as an ion conductive layer and as an electronic conductive layer.
• the low porosity of the continuous phase allows the active particles to go through a volume change in the lithiation/delithiation (Li/DeLi) cycles without experiencing substantial mechanical degradation, while maintaining their protection/isolation from the porous phase. This limits formation of extensive solid electrolyte interface (SEI) build up and holds any possible fragments in close proximity.
• SEI solid electrolyte interface
• the low porosity of the electrode presents a problem in terms of cell functionality.
• the porosity of the continuous phase must be selected to, on one end, permit effective transport of the ions to the active materials and, at the same time, prevent wetting of the active materials.
• Too low a porosity causes a reduction in the effective surface area available for such interaction, and hence increases internal resistance (i.e., reduces the energy efficiency of the system since part of the energy is translated into heat due to the resistance). Low porosity also reduces the apparent capacity as some of the active material is not accessible to tiie lithium ion flux, and hence promotes faster degradation of the electrode and the cell as a whole.
• the ionic transport becomes available, while at higher C rates (higher currents, higher flux) the ionic transport becomes reduced due to blocking, hence even faster degradation occurs.
• metallization forms on the electrode since more ions arrive to the available liquid/solid interface than capable to penetrate into the active material.
• the rate of lithium ions transport to the solid/electrolyte interface is larger than the rate of lithium ion transport into the active material, while the rate of lithium reduction increases and hence lithium ions are reduced to metal lithium on the available surface area.
• de-solvation of the lithium ions occurs mostly at the interface (the separation region, the separator) between the electrolyte solution and the ion conductive polymer, where the ions then transport via the ion conductive polymer to the active material in a partially charged mode, which reduces the probability for metallization.
• the continuous phase in an electrode of the invention is constructed of at least one highly ion conductive substance that display low electronic conductivity.
• the ion conductive substance is at least one ion conductive polymeric material, as further detailed herein.
• Non-limiting examples of the ion conductive polymers may be selected from polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyethylene imine (PEI), lithium polyacrylic acid (LiPAA), polyacrylic acid (PAA), lithium polyphosphate (LiPP), poly ammoniumphosphate (APP), polyphosphates, polyvinylpyrrolidone (PPy), polysaccharide-based polymers, such as carboxymerhyl cellulose (CMC), lithium alginate (LiAlg), alginate (Alg), methyl-cellulose (MC) and sulfonated cellulose (SC) and any derivatives or combinations thereof.
• CMC carboxymerhyl cellulose
• LiAlg lithium alginate
• Alg alginate
• the material(s) of the continuous phase does not promote SEI formation on their surface, so that the first cycle efficiency in lithium ion battery remains as high as possible.
• the electrodes can also combine other ion conductive materials which exhibit electronic conductivity. Such materials may be, for example, PEDOT:PSS, PANi, National, which can be integrated in the matrix as co-binders and/or as possible pre-coating materials for the active materials.
• the electrode can also combine additional non-conductive polymers, with a total of less than 5% of the electrode material, to promote better adhesion and cohesion, if necessary.
• Such polymers may be, for example, polyvinylidene fluoride (PVDF), styrene butadiene (SBR) and others.
• the active material particles are selected based on the function of the ICA.
• An electrode of the ICA can be made from highly ion conductive materials and very low electronic conductive continuous phase, which connects the active material particles and the conductive additives.
• the active material may be selected from a group of materials which can adsorb cations such as, but not limited to lithium, by for example intercalation or alloying.
• the active material is typically provided in tire form of particles which may be selected from microparticles, nanoparticles, nanotubes, nanowires or of any other nanometric architecture.
• the active material may be of a material selected from carbonaceous materials such carbon allotropes, e.g., graphite, graphene, CNT, carbon black, and others; and elemental materials such as silicon, germanium, tin, lead, aluminum, and/or their oxides.
• carbonaceous materials such as graphite, graphene, CNT, carbon black, and others
• elemental materials such as silicon, germanium, tin, lead, aluminum, and/or their oxides.
• Non-limiting examples of such materials include graphite of any type, composite graphite material of any kind, silicon nanoparticles (SiNP) or nanowires (SiNW) of any morphology, composite anode material of any kind, such as silicon-graphite, silicon- carbon, silicon oxide, and any metalloid-carbon (of any form, such as graphene etc.) and/or metalloid-graphite, germanium nanoparticles or nanowires, tin nanoparticles or nanowires, lithium nanoparticles, lithium microparticles and any combination thereof.
• SiNP silicon nanoparticles
• SiNW nanowires
• the active material particles may be selected from conductive carbonaceous materials such as, but not limited to, carbon black (such as Super C45, Super C65), Single walled carbon nanotubes (SWCNTs), multiwalled carbon nanotubes (MWCNTs), Graphite, tungsten carbide and others.
• the active material may be selected from lithium salts such as LiFePO 4 (lithium ferro phosphate), lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium nickel oxide (LNO), lithium cobalt oxide (LCO) and any combination thereof.
• the cathode may further comprise conductive additives such as carbonaceous materials, e.g., carbon black (such as Super C45, Super C65), SWCNTs, MWCNTs, Graphite, WC and others.
• the separator does not comprise active materials or electron conductive additives, it may comprise particles of ion conductive substances, ion conductive salts and further ceramic nano- or micro-particles.
• the purpose of these materials is to better ion conductivity, to act as lithium metal dendrite quencher (and hence afford better stability and higher safety) and/or provide a more rigid structure.
• the electrode of the invention SE1 formation on the active material surface is greatly reduced, thereby also reducing lithium loss. Furthermore, due to the low porosity of the electrode, the liquid electrolyte in the porous phase cannot reach every part of the continuous phase (continuous phase), thus the reactive surface area of tire binder in the electrode is reduced in comparison to commonly used binders, without compromising the needed ionic mobility. This also enables the use of smaller amounts of the electrolyte solution as compared to regular lithium ion batteries since the mosaic electrode (anode or cathode) can hold much less electrolyte solution than a regular electrode.
• the electrode is highly effective mainly when using metalloids as active materials, since this highly ionic conductivity serves as an artificial SE1 layer which protects the active material from liquid electrolyte solutions, and hence further increases the first cycle efficiency and reduces the adverse side reactions and the lithium consumption. Due to the flexibility of the ion conductive materials, any expansion and/or break of the active material during cycling, is absorbed within the matrix of the electrode, with a minimal (if any) exposure of the newly formed active material surfaces to the electrolyte solution, and hence additional SEI formation is limited. Since these breakings occur in highly ion conductive surroundings, the limited loss of effective surface area is minimal during the process. Furthermore, since the conductive additives are also embedded in this continuous layer, the SEI formation on top of them is also limited to negligible.
• the use of the ICA of the present invention gives rise to systems with a high first cycle efficiency, higher cycle life, and limits the need for pre-lithiation, in comparison to known technologies.
• the ICA further allows for the use of metalloids as anodes in much higher concentrations in the anodes than current practices.
• Electrode compositions of the invention may be selected as depicted in Scheme 1 below.
• an active material may be selected with a conductive additive material and a conductive polymer to provide an ion conductive phase.
• graphite may be used as an active material alone with PEI as the ion conductive polymer with CNTs as conductive additives.
• the gray lines indicate possible material selection for anode electrodes, and the black lines are for cathode electrode area. Dashed lines are optional additions. It is to be noted that anodes and cathodes having the configuration disclosed herein can exist independent one of the other, but can be combined for forming a path for ions from the anode to the cathode and vice versa.
• the present invention further provides a method for producing an ICA of the present invention.
• an electrode being an anode or a cathode, is prepared using an ion conductive binder.
• the method includes preparation of slurry comprising an active material and an ion conductive polymer.
• the slurry may further comprise at least one binder, optionally in the form of one or more additional polymer.
• the slurry may be pre -prepared or may be formed just before the ICA is fabricated.
• the slurry is first spread (e.g., by using Dr. blade) on a substrate being, in some embodiments, a battery grade copper foil for anodes, or battery grade aluminum foil for cathodes, dried, and then pressed to achieve a porosity smaller or equal to 20%.
• porosity control can be achieved by using, for example, hot roll press (calandering machine), or any other press mechanism known to art. Additional control over tire porosity before and/or after pressing, or without press, can be achieved by ultrasonic cavitation, direct printing mechanism, or controlled electrophoretic deposition.
• a separator film (being the separation area discussed herein) is formed on tire electrode film by, e.g., spreading, a highly lithium ion conductive polymer.
• the conductive polymer may or may not be the same used in the anode and/or the cathode.
• the separation area may further comprise ceramic particles of a material such as titanium oxide, aluminum oxide, and others, as detailed herein.
• a method of the invention comprises:
• the electrode anode or cathode
• the electrode as a thin film having a porosity up to 20%, as defined herein, on a substrate, being a metal film, or any other electron conductive substrate (in some embodiments, the film being 1 to about 150 micrometer thick); and -forming a separator film on said electrode, the separator film having a porosity between 20% and 80%, or between 40 and 60%.
• the method comprises obtaining a slurry comprising an active material and an ion conductive polymer.
• the slurry further comprises at least one additive such as at least one binder, at least one surfactant, at least one deflocculant and optionally other additives, wherein the additives are optionally in the form of one or more additional polymer.
• the at least one surfactant acts as a deflocculating agent such as sodium hexametaphosphate (SHMP).
• the slurry is formed by adding conductive additives into a dissolved binder solution, followed by adding the active material.
• the slurry is formed by gradually adding conductive additives into a dissolved binder solution while mixing at low speed (>100rpm), then mixing at 1200rpm for 1 hour (premix stage) then gradually adding the active material during slow mixing (>100rpm), followed by 1 hour mixing at 1200rpm. Then mixing is continued at 600rpm (kneading).
• the amount of the active material is between 85 and 95%, conductive additive between 0.5 and 3%, and conductive polymer/binder in an amount between 1 and 12% (w/w).
• the amount thereof is between 40 and 70%, the amount of the conductive additive is between 10 and 40%, and the amount of the ion conductive binder is between 10 and 40% (w/w).
• the amount of the active material is 93%, conductive additive 2%, and conductive polymer/binder 5% (w/w).
• the electrode film is formed to reduce the pores in the film to a bare minimum.
• the porosity of the electrode film is below or up to 20%. In some embodiments, it is below 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 or 2%.
• the low porosity is typically achieved by spreading the slurry on the substrate, e.g., metallic substrate, and pressing the spread slurry to achieve the required porosity.
• the measurements performed for estimating porosity include electrode thickness (without the current collector) and electrode weight per unit area.
• the initial (e.g. after spreading and drying) porosity is usually between 45% to 70%. Calculation is done for the thickness of the electrode needed to receive, with the same weight per area, the required porosity.
• the roll press is set to the required thickness (which is smaller than the initial thickness) and the electrode is passed through.
• the slurry may be applied onto the substrate by any one of the following methods printing (of any kind), electrophoretic deposition (EPD), electromagnetic depositing (EMD) when the particles are, or coated by ferromagnetic substance, spin coating, atomic layer deposition (ALD) and others.
• printing of any kind
• EPD electrophoretic deposition
• EMD electromagnetic depositing
• spin coating spin coating
• ALD atomic layer deposition
• the electrode comprises multiple material films.
• a method of the invention comprises forming a first electrode film on a substrate, drying said first electrode film; applying a further amount of a slurry (same or different from the slurry of the first electrode film) on the dried first electrode film, drying same and repeating one or more times to obtain the multilayer.
• the separator film may be formed on the top most electrode film.
• the method of the invention further provides a method for constructing an electrode assembly (or a hybrid electrode) comprising both an anode and a cathode.
• an anode or a cathode may be formed as described herein, followed by forming a separator film on the electrode. Subsequently, the separator film may be coated with a material composition (a slurry) of the opposite electrode.
• This method may thus comprise:
• anode or a cathode electrode as a first thin film having a porosity below 20%, as defined herein, on a substrate, being a metal film, or any other electron conductive substrate (in some embodiments, the film being 1 to about 150 micrometer thick);
• separator film on said anode or cathode, the separator film having a porosity between 20% and 90%;
• the first thin film is an anode film and the second thin film is a cathode film. In other embodiments, the first thin film is a cathode film and the second thin film is an anode film.
• the ion conductive polymer making up the separator may be the same as the ion conductive polymer of either or both the anode and cathode film, or may be different from both.
• Each of the anode and cathode electrodes has its own current collector.
• the deposition of the films can be in sequence.
• an LBL method may be applied in which a 1 st electrode on current collector, followed by separation layer, flowed by 2 nd electrode and ending with the 2 nd current collector which can be deposited by any method from printing, to spreading or attaching.
• the 1 st electrode is deposited on its current collector, following by separation area depositing.
• the 2 nd electrode is similarly associated with a current collector, and then the two separator @ electrode films are attached together by adhesion.
• the separator film is adhesively associated with the electrode film such that the two films are mechanically inseparable.
• the separator is formed by applying a solvent mixture comprising of at least one ion conductive polymer.
• the ion conductive polymer used may be the same or different from that used in the electrode.
• a desired porosity can be achieved by using, e.g., a hot roll press (calendaring machine), or any other press mechanism known in the art. Additional control over the porosity before and/or after pressing, or without press, can be achieved by ultrasonic cavitation, direct printing mechanism, or controlled electrophoretic deposition. Controlling the porosity before and/or after pressing, or without press, can also be achieved by ultrasonic cavitation.
• Theoretical calculation for porosity estimation is based on the bulk density of the substances. The measurements done for this estimation are electrode thickness (without the current collector) and the weight per unit of area. The initial (e.g., after spreading and drying) porosity is usually between 45% to 70%. Calculation is done fra: the thickness of the electrode needed to achieve, with the same weight per area, the required porosity. When roll pressing is used, it is set to the required thickness and the electrode is passed through to receive the desired electrode thickness which is matching the desired porosity.
• an energy storage device comprising ICA of the present invention.
• the energy storage device of the invention comprises at least one energy cell.
• the energy cell may comprise an electrode of the invention, which may be in a form of anode and/or a cathode or an hybrid electrode (an assembly of both an anode and a cathode separated by a separator, as disclosed herein) and an electrolyte solution.
• the energy cell comprises an anode or a cathode constructed as disclosed herein.
• the energy cell comprises a hybrid electrode, as disclosed herein.
• the electrolyte solution comes into contact with the separator or in the case of the hybrid electrode with the separation area and has little or no interaction with the active material present in the electrode.
• an energy storage device is a device that stores energy for later use.
• the device is typically a battery that may be chargeable or non-rechargeable.
• the devices of the invention may be selected from lithium batteries, sodium batteries, magnesium batteries or any other battery and combination thereof.
• the invention additionally provides a lithium battery comprising an ICA of the invention.
• the electrode film in the ICA of the lithium battery is an anode.
• the invention also contemplates an electrode comprising a low porosity continuous ion conductive polymeric material and one or more active materials, as disclosed herein.
• the electrode may be one comprising a current collector having on at least a region thereof a film of at least one ion conductive material having a porosity below 20% and comprising a plurality of active materials fully embedded within the ion conductive material, the film of the at least one ion conductive material being configured to surface associate to a separator film comprising at least one ion conductive material, having a porosity of between 20 and 80%, and being free of active materials and electron conductive additives.
• the electrode is an anode.
• the electrode of the invention may be used in fabricating an ICA of a structure defined herein or any other generic ICA as may be known in the art.
• Figs. 1A-B provide schematic depictions of an anode according to the invention.
• Fig. 1A is a general schematic depiction of anode and an ion conductive separator in a LPML structure.
• Fig. IB is a theoretical representation of an ion flux in an anode structure having an ion conductive separator in a LPML structure of the invention.
• Fig. 2 is an image of an anode and an ion conductive separator in a LPML structure.
• Figs. 3A-C provide: Fig. 3A - a PVDF-based anode half-cell with and without ICM (Example lb & Example 3). First formation cycle at 0.03C.
• Fig.3B - a PVDF based anode half-cell with and without ICM (Example lb & Example 3).
• Fig. 3C - a PVDF based anode half-cell with and without ICM Example lb & Example 3).
• Figs. 4A-D provide: Fig. 4A - a CMC based anode half-cell with and without ICM (Example la & Example 4). First formation cycle at 0.03C. Fig. 4B - a CMC based anode half-cell with and without ICM (Example la & Example 4). Last formation cycle at 0.1C. Fig. 4C - a CMC based anode half-cell with and without ICM (Example la & Example 4). Formation cycles coulombic efficiency: regular stabilization is seen in all samples. Fig. 4D - a CMC based anode half-cell with and without ICM (Example la & Example 4).
• Fig. 5 depicts the discharge capacity rate (%) vs cycle ID comparison between example 1a, 1b with regular separator and ICS separator at 0.5C cycling (cycles following the formation).
• the anodes are pressed to ⁇ 10%, and with comparison to 30% porosity anode with ICS separator area.
• the stability of the ion conductive polymer-based binder anode with ⁇ 10% anode porosity, and with ICS separator is the greatest in comparison with all ⁇ 10% porosity anodes, and even better stability than 30% (regular) porosity anode.
• Electrolyte 1.1M LiPF 6 in EC:EMC (3:7) 1 %(w/w) LiPO 2 F 2 , 1%(w/w) VC.
• Regular separator 12um thickness Polypropylene separator.
• the spread anode was dried at 60 °C for 5 hours and then additional 12 hours at
• the resulting electrode was pressed to achieve a porosity of 30%, 7-8%, and ⁇ 5% porosity.
• the resulting electrode was pressed to achieve a porosity of 30%, and ⁇ 10% porosity.
• LiPAA 13 wt. % solution was added into 36 mL of 2D-H 2 O, followed by addition of 0.2125 g of short ammonium polyphosphate ( ⁇ 100 units polymer) and 0.1 g of sodium hexametaphosphate (SHMP) and mixed to full dissolution. Then, 20 g of 5- 8 mm alumina particles were added and mixed for 12 hours prior to use.
• Example 2 The mixture was spread on an anode prepared in Example 1 using a 405- micrometer gap“Dr. Blade”, dried at 60 °C for 1 hour, followed by drying at 100 °C for 12 hours prior to testing.
• Example 2 The mixture was spread on anodes prepared in Example 1 using a 230-micrometer gap“Dr. Blade”, dried at 60 °C for 1 hour, followed by drying at 100 °C for 12 hours prior to testing.
• Example 6 Preparation of Ion Conductive Separation Area 6 and ICA Using it
• Example 2 The mixture was spread on an anode prepared in Example 1 using a 230- micrometer gap“Dr. Blade”, dried at 60 °C for 1 hour, followed by drying at 100 °C for 12 hours prior to testing.

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• 2020
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